Measurement of the OH reaction rate constants for CF3CH2OH, CF3CF2CH2OH, and CF3CH(OH)CF3

被引:60
作者
Tokuhashi, K
Nagai, H
Takahashi, A
Kaise, M
Kondo, S
Sekiya, A
Takahashi, M
Gotoh, Y
Suga, A
机构
[1] Natl Inst Mat & Chem Res, Dept Chem Phys, Tsukuba, Ibaraki 305, Japan
[2] Res Inst Innovat Technol Earth, Bunkyo Ku, Tokyo 113, Japan
关键词
D O I
10.1021/jp983961x
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The OH reaction rate constants have been measured for CF3CH2OH, CF3CF2CH2OH, and CF3CH(OH)CF3 over the temperature range 250-430K. Kinetic measurements have been carried out using the discharge flow, laser photolysis, and flash photolysis methods, combined respectively with the laser-induced fluorescence technique to monitor the OH radical concentrations. The influence of impurities contained in the sample of CF3CF2CH2OH has been investigated by means of sample purification using gas chromatography. No sizable effect of impurities was found on the measured rate constants of these three fluorinated alcohols. The Arrhenius rate constants have been determined from the respective kinetic data as k(CF3CH2OH) = (2.00 +/- 0.37) x 10(-12) exp[-(890 +/- 60)/T], k(CF3CF2CH2OH) = (1.40 +/- 0.27) x 10(-12) exp[-(780 +/- 60)/T], and k(CF3CH(OH)CF3) = (6.99 +/- 1.56) x 10(-13) exp[-(990 +/- 70)/T] cm(3) molecule(-1) s(-1). A method of predicting the OH reaction rate constants for fluorinated alcohols, hydrofluorocarbons, alkanes, and alcohols has been proposed.
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页码:2664 / 2672
页数:9
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