Atmospheric chemistry of perfluorinated aldehyde hydrates (n-CxF2x+1CH(OH)2, x=1, 3, 4):: Hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation

被引:21
作者
Andersen, M. P. Sulbaek
Toft, A.
Nielsen, O. J.
Hurley, M. D.
Wallington, T. J.
Chishima, H.
Tonokura, K.
Mabury, S. A.
Martin, J. W.
Ellis, D. A.
机构
[1] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen, Denmark
[2] Univ So Denmark, Dept Chem, DK-5230 Odense M, Denmark
[3] Ford Motor Co, Dearborn, MI 48121 USA
[4] Univ Tokyo, Environm Sci Ctr, Bunkyo Ku, Tokyo 1130033, Japan
[5] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada
关键词
D O I
10.1021/jp060404z
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
Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+CxF2x+1CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+ CxF2x+1CH(OH)(2)) (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N-2 or air at 296 +/- 2 K. The Cl initiated oxidation of CF3CH(OH)(2) in 700 Torr of air gave CF3COOH in a molar yield of 101 +/- 6%. IR spectra of CxF2x+1CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF3CHO+H2O) < 2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF3CHO. Bubbling CF3CHO/air mixtures through liquid water led to > 80% conversion of CF3CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of CxF2x+1CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.
引用
收藏
页码:9854 / 9860
页数:7
相关论文
共 30 条
[1]   Atmospheric chemistry of n-CxF2x+1CHo (x=1,3,4):: Mechanism of the CxF2x+1C(O)O2+HO2 reaction [J].
Andersen, MPS ;
Stenby, C ;
Nielsen, OJ ;
Hurley, MD ;
Ball, JC ;
Wallington, TJ ;
Martin, JW ;
Ellis, DA ;
Mabury, SA .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (30) :6325-6330
[2]   Atmospheric chemistry of n-CxF2x+1CHO (x=1, 3, 4):: Reaction with Cl atoms, OH radicals and IR spectra of CxF2x+1C(O)O2NO2 [J].
Andersen, MPS ;
Nielsen, OJ ;
Hurley, MD ;
Ball, JC ;
Wallington, TJ ;
Stevens, JE ;
Martin, JW ;
Ellis, DA ;
Mabury, SA .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (24) :5189-5196
[3]   Atmospheric chemistry of CH3O(CF2CF2O)nCH3 (n=1-3):: Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials [J].
Andersen, MPS ;
Hurley, MD ;
Wallington, TJ ;
Blandini, F ;
Jensen, NR ;
Librando, V ;
Hjorth, J .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (11) :1964-1972
[4]   Atmospheric chemistry of C2F5CHO:: reaction with Cl atoms and OH radicals, IR spectrum of C2F5C(O)O2NO2 [J].
Andersen, MPS ;
Hurley, MD ;
Wallington, TJ ;
Ball, JC ;
Martin, JW ;
Ellis, DA ;
Mabury, SA ;
Nielsen, OJ .
CHEMICAL PHYSICS LETTERS, 2003, 379 (1-2) :28-36
[5]  
Atkinson J, 1997, PERCEPTION, V26, P763
[6]  
ATKINSON R, IUPAC SUBCOMMITTEE G
[7]  
Calvert J.G., 2000, The mechanisms of atmospheric oxidation of the alkenes
[8]  
Calvert J.G., 1966, Photochemistry
[9]   Mechanism and dynamics of the CH2OH+O2 reaction [J].
Dibble, TS .
CHEMICAL PHYSICS LETTERS, 2002, 355 (1-2) :193-200
[10]   Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment [J].
Ellis, DA ;
Mabury, SA ;
Martin, JW ;
Muir, DCG .
NATURE, 2001, 412 (6844) :321-324