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Rotating sector study of the gas phase photochlorination of 2,2-dichloro-1,1,1-trifluoroethane

✍ Scribed by R. F. Cullison; R. C. Pogue; M. L. White

Publisher
John Wiley and Sons
Year
1973
Tongue
English
Weight
413 KB
Volume
5
Category
Article
ISSN
0538-8066

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✦ Synopsis

The rate constant for the combination of 2,2-dichloro-l,1 ,I-trifluoroethyl radicals has been measured by applying the rotating sector technique to the gas phase photochlorination of 2,2-dichloro-l,l,l-trifluoroethane at 315°K. The observed value is 6.89 X 10' 2 cc/rnole .set. This value is in excellent agreement with measurements by Wampler and Kunrz which yielded a temperature-independent value of 6.6 X lo1* cc/mole.sec. The measurement by Wampler and Kuntz was determined from the photochemical system (CF3CC13 + C-CsH,2 f hv). The Arrhenius parameters for the reaction CFaCC12. + Clt + CPsCCl3 + C1 were found to be given by the expression log k3 = 12.10 -5830/2.3RT (units in mole, cc, and sec). This is a relatively high activation energy for a chlorination reaction and makes the reaction ever slower than the chlorination of chloroform.

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