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.
ZHEJIANG JIANYE CHEMICAL CO.,LTD.
Contact:86-571-64149273,64149234
Address:No. 48, Fuxi Road, Meicheng Town
Xinjiang Zhongtai Chemical Co., Ltd.
Contact:+86-991-8788172
Address:NO.78 XISHAN RD.URUMQI，CHINA
Contact:+86-021-50792271
Address:Building 24A, 300 Chuantu Road, Chuansha, Pudong new area, Shanghai, China, 201202
Hangzhou JINLAN Pharm-Drugs Technology Co., Ltd
website:http://www.jlpharms.com
Contact:86-571-86982636
Address:Rm A606, Fuyi Center, jianqiao street
Shanghai Balmxy Pharmaceutical Co., Ltd
Contact:0086-21-24206007
Address:Room 402, 15#, No. 909 wangyue Road, shanghai, P. R. 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)
