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Arrhenius parameters for reactions of oxygen atoms with the fluorinated ethylenes

✍ Scribed by D. S. Jones; S. J. Moss

Publisher
John Wiley and Sons
Year
1974
Tongue
English
Weight
428 KB
Volume
6
Category
Article
ISSN
0538-8066

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✦ Synopsis

Competitive studies of the reactions of ground-state oxygen atoms, generated by mercury-photosensitized decomposition of nitrous oxide, have been carried out with ethylene and all the fluoroethylenes using 2-(trifluoromethy1)-propene as reference compound. From measurements at 25Β°C and 150Β°C relative rate constants have been determined and used to calculate the Arrhenius parameters shown in the following table:

03 0.84 0.94 2.02 CH2=CF2 0.71 I .49 0.65 2.67 CHF=CHF (cis-) 1.23 I .92 1.12 3.10 CHF=CHF (trans-) 1 .40 0.79 I .27 1.97 CF2=CHF 1.06 0.00 0.96 1.22 CF2=CFz 0.86 -3.22 0.78 -2.04 AE'Ref = Eolef,n -E 2 = ~~p and aECZH4 = Eolefin -E c ~H ~. Units are kJ/mole.

The results are compared with corresponding data for other atoms and radicals, and discussed in terms of the electronic changes produced in the double bond by fluorine substitution, and in relation to the nature of the transition state.

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