Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1471 - 1482 (1985)
Update date:2022-08-17
Topics:
Kerr, J. Alistair
Wright, J. Paul
The kinetics and pressure dependence of the decomposition of the trifluoroacetyl radical: CF3CO+M->CF3+CO+M (5') have been studied by generating the radicals from the selective photolysis of azomethane in the presence of 1,1,1-trifluoroacetaldehyde over the temperature range 338-417 K.The rate constants of the decomposition reaction (k5') have been measured relative to the radical combination reactions: CH3+CF3CO->CF3COCH3 (6) 2CH3->C2H6 (2).The rate constants (k5'), were found to be pressure-dependent over the pressure range 50-740 Torr, with SF6 as a bath gas.The A factor of the radical decomposition reaction has been calculated from transition-state theory to be A5'<*> ca. 2.2E13 s-1.Treatment of the pressure dependence of the rate constants (k5'), according to the RRKM theory of unimolecular reactions, yielded a high-pressure limiting activation energy E5'<*>=83.1 kJ mol-1.Thus the present data consistent with a high-pressure limiting Arrhenius expression: log(k5'<*>/s-1)=(13.34+/-0.8)-<(10000+/-1000)/2.303T> where the error limits are estimates of the accuracies of the Arrhenius parameters.The results are discussed in relation to existing data on the CF3CO radical and are compared with kinetic data on the decomposition reactions of the CH3CO and C2H5CO radicals.
Nanjing Capatue Chemical Co., Ltd
Contact:+86-25-86371192 +86-025-85720158
Address:No.20 Jiangjun Avenue, Jiangning Economic & Technical Development Zone
Shanghai Sinofluoro Scientific Co., Ltd
Contact:+86-21-64279360
Address:Room 1006,Building 3,#58 East Xinjian Road, Shanghai ,201100,China,
NINGBO YINZHOU PRECISE COLOR CO.,LTD.
Contact:86-574-88139809 86-574-83033159
Address:Qiming Road,Yinzhou,Ningbo,China
Contact:+49-4101-3053-0
Address:Waldhofstrasse 14 ,25474 Ellerbek Germany
Zhejiang Chemicals Import & Export Corporation
Contact:86-571-87043088
Address:No.37,Qingchun Road,Hangzhou,China
Doi:10.1002/pola.24055
(2010)Doi:10.1021/jo01277a057
(1967)Doi:10.1021/jp972767s
(1998)Doi:10.1021/jacs.0c00326
(2020)Doi:10.1021/ja01070a042
(1964)Doi:10.1021/ja01184a050
(1948)
