Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes

被引:85
作者
Hurley, MD
Andersen, MPS
Wallington, TJ
Ellis, DA
Martin, JW
Mabury, SA
机构
[1] Ford Motor Co, Dearborn, MI 48121 USA
[2] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada
关键词
D O I
10.1021/jp036343b
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
Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0.03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric fate of F(CF2)(n)COOH. The major atmospheric removal mechanism for F(CF2)(n)COOH is believed to be wet and dry deposition which probably occurs on a time scale of the order of 10 days.
引用
收藏
页码:615 / 620
页数:6
相关论文
共 50 条
[1]  
Atkinson R, 2000, HANDBOOK OF PROPERTY ESTIMATION METHODS FOR CHEMICALS, P335
[2]   Environmental risk assessment of trifluoroacetic acid [J].
Boutonnet, JC ;
Bingham, P ;
Calamari, D ;
de Rooij, C ;
Franklin, J ;
Kawano, T ;
Libre, JM ;
McCulloch, A ;
Malinverno, G ;
Odom, JM ;
Rusch, GM ;
Smythe, K ;
Sobolev, I ;
Thompson, R ;
Tiedje, JM .
HUMAN AND ECOLOGICAL RISK ASSESSMENT, 1999, 5 (01) :59-124
[3]   The Henry's law constant of trifluoroacetic acid and its partitioning into liquid water in the atmosphere [J].
Bowden, DJ ;
Clegg, SL ;
Brimblecombe, P .
CHEMOSPHERE, 1996, 32 (02) :405-420
[4]   WET REMOVAL OF HIGHLY SOLUBLE GASES [J].
BRIMBLECOMBE, P ;
DAWSON, GA .
JOURNAL OF ATMOSPHERIC CHEMISTRY, 1984, 2 (01) :95-107
[5]  
Calvert J. G., 2000, MECHANISMS ATMOSPHER
[6]   KINETICS AND MECHANISMS FOR THE REACTION OF HYDROXYL RADICALS WITH TRIFLUOROACETIC-ACID UNDER ATMOSPHERIC CONDITIONS [J].
CARR, S ;
TREACY, JJ ;
SIDEBOTTOM, HW ;
CONNELL, RK ;
CANOSAMAS, CE ;
WAYNE, RP ;
FRANKLIN, J .
CHEMICAL PHYSICS LETTERS, 1994, 227 (1-2) :39-44
[7]   ASSOCIATION OF TRIFLUOROACETIC ACID IN VAPOR AND IN ORGANIC-SOLVENTS [J].
CHRISTIA.SD ;
STEVENS, TL .
JOURNAL OF PHYSICAL CHEMISTRY, 1972, 76 (14) :2039-&
[8]  
Crowder G. A, 1972, J FLUORINE CHEM, V1, P385, DOI DOI 10.1016/S0022-1139(00)82959-0
[9]   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
[10]  
ELLIS DA, 2002, HDB ENV CHEM N, V3