Kinetics and mechanism of IR laser-induced transformations of CF3CHClF

Chemical reactions due to the action of pulsed IR radiation on CF3CHClF wer e studied. The Arrhenius parameters for the rate equation of unimolecular t hree-centered dehydrochlorination (E-a1 = 247.9 +/- 10.5 kJ/mol, A(1) = 10( 12.1) s(-1)) and four-centered dehydrofluorination (E-a2 = 293.2 + 14.6 kJ/ mol, A(2) = 10(13.09) (+/-) 0.7 s(-1)) were determined for CF3CHClF It was shown that the formation of n-C3F6 is due to the cross combination of carbe nes produced by either primary or secondary degradation of the starting com pound. The obtained product ratio can quantitatively be rationalized only i f the isomerization reaction of :CFCF3 is taken into account.