Premium
Rotating sector study of the gas phase photochlorination of 2,2‐dichloro‐1,1,1‐trifluoroethane
Author(s) -
Cullison R. F.,
Pogue R. C.,
White M. L.
Publication year - 1973
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550050311
Subject(s) - chemistry , chloroform , arrhenius equation , gas phase , mole , activation energy , radical , phase (matter) , reaction rate constant , medicinal chemistry , analytical chemistry (journal) , organic chemistry , kinetics , physics , quantum mechanics
The rate constant for the combination of 2,2‐dichloro‐1,1,1‐trifluoroethyl radicals has been measured by applying the rotating sector technique to the gas phase photochlorination of 2,2‐dichloro‐1,1,1‐trifluoroethane at 315° K . The observed value is 6.89 × 10 12 cc/mole.sec. This value is in excellent agreement with measurements by Wampler and Kuntz which yielded a temperature‐independent value of 6.6 × 10 12 cc/mole.sec. The measurement by Wampler and Kuntz was determined from the photochemical system (CF 3 CCl 3 + C‐C 6 H 12 + hν). The Arrhenius parameters for the reaction CF 3 CCl 2 · + Cl 2 → CF 3 CCl 3 + Cl were found to be given by the expression log k 3 = 12.10 − 5830/2.3 RT (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.