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Kinetics of the reactions of halogenated methyl radicals (CF3, CF2Cl, CFCl2, and CCl3) with molecular chlorine

✍ Scribed by Raimo S. Timonen; John J. Russell; David Gutman

Publisher: John Wiley and Sons
Year: 1986
Tongue: English
Weight: 570 KB
Volume: 18
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550181008

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✦ Synopsis

The kinetics of four gas-phase reactions involving halogenated methyl radicals (R,==CF,, CF2C1, CFCI,, and eel,) with molecular chlorine have been studied using a tuhular reactor coupled to a photoionization mass spectrometer. The radicals were homogeneously generated by the pulsed photolysis of precursor molecules at 193 nm. The subsequent decays of the radical concentrations were monitored in real-time experiments as a function of Clz concentration to obtain the rate constants of these R + C1, reactions.

Where possible, the rate constants were measured as a function of temperature to determine Arrhenius parameters. Apparent discrepancies between these measiired rate constants for CF, and CCl, with Clz and ones obtained in prior indirect studies are explained.

The higher activation energies for these R + Clz reactions compared to that of the CH, + Clz reaction are attributed in part to the different polarities of the transition states formed.

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