par Goldfinger, Paul 
;Huybrechts, Guy ;Martens, G.
Référence Transactions of the Faraday Society, 57, page (2210-2219)
Publication Publié, 1961
;Huybrechts, Guy ;Martens, G.Référence Transactions of the Faraday Society, 57, page (2210-2219)
Publication Publié, 1961
Article révisé par les pairs
| Résumé : | The gas-phase photochlorinations of mixtures of tetrachloroethylene with methane, methyl chloride, methylene chloride, chloroform and pentachloroethane have been studied in a static system. Reaction rates have been followed manometrically and photometrically. This technique permitted us to measure two elementary rate constants C2Cl4+Cl→C 2Cl5 (2); log k2=9.4, C2Cl 5H+Cl→C2Cl5+HCl(2′); log k′2=-723/T+9.8. Further experiments permitted us to measure the complex rate constant log (k′2k4/k 2k3)1/2=-1605/T+2.50, where k3 and k4 refer to the elementary reactions, C2Cl 5+Cl2→C2Cl6+Cl (k3) C2Cl5→C2Cl4+Cl.(k4) Using the results of the preceding paper and the calculated equilibrium constants for the chlorination of C2Cl4 and C 2Cl5H, all the eight elementary constants determining the rate of these photochlorinations have been calculated. Numerous cross-checks can further be performed and show complete agreement. Incidentally, the relative values of the rate constants for hydrogen abstraction from CH4, CH3Cl, CH2Cl2, CHCl3 measured previously by Knox have been checked. |
