Nov. 5, 1956 COMMUNICATIONS 5697 kl is a constant at constant

5, 1956. COMMUNICATIONS. TO THE EDITOR. 5697. CHs + isooctane + CHI + isooctyl radical. CH, + olefin + olefinCH8 k1 kp kl is a constant at constant ...
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COMMUNICATIONS TO THE EDITOR

Nov. 5, 1956 CHs CH,

+ isooctane +CHI + isooctyl radical

+ olefin +olefinCH8

k1

4,

- E1 - E1

= -0.6 kcal./mole

A ~ / A I= 13.0

= -2.8 kcal./mole

A2/A1 = 5.3

The reactivity of tetrachloroethylene is too low to determine the activation energy with any reasonable accuracy. We conclude t h a t the reactivity of tetrafluoroethylene is approximately ten times greater than t h a t of ethylene, while tetrachloroethylene is unreactive. The higher reactivity of tetrafluoroethylene is shown to result from the lower activation energy of the addition reaction (as compared with ethylene), while the AZ/A1 factor is lower for the reaction involving tetrafluoroethylene than that for ethylene. The methyl affinity of ethylene is comparable to that of vinylacetate, is approximately 80 times greater than t h a t of benzene and l / 2 6 as large as that of styrene. TABLEI Compound

T, ‘C.

kdki

Ethylene Ethylene Ethylene Ethylene Tetrafluoroethylene Tetrafluoroethylene Tetrafluoroethylene Tetrafluoroethylene Tetrachloroethylene

54.7 64.9 74.8 85.2 54.7 64.9 74.8 85.2 64.9

37 3 f 0.6 34.1 f 2 . 2 34.6 f 0.6: 35.5 f 1 . 5 400 f 7 342 f 14 307 rt 8 273 f 8