Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

被引：37
作者：
Teruel, Mariano A. [1 ]
Blanco, Maria B. [1 ]
Luque, Gabriela R. [1 ]
机构：
[1] Univ Nacl Cordoba, Fac Ciencias Quim, INFIQC, Dpto Fisicoquim, RA-5000 Cordoba, Argentina
来源：
ATMOSPHERIC ENVIRONMENT | 2007年 / 41卷 / 27期
关键词：
acrylic acid; acrylonitrile; rate coefficients; addition reactions; tropospheric chemistry;
D O I：
10.1016/j.atmosenv.2007.02.028
中图分类号：
X [环境科学、安全科学];
学科分类号：
08 ; 0830 ;
摘要：
Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm(3) molecule(-1) s(-1)): k(1)(OH+CH2 = CHC(O)OH) = (1.75 +/- 0.47) x 10(-11) , k(2)(Cl + CH2 = CHC(O)OH) = (3.99 +/- 0.84) x 10(-10), k(3)(OH + CH2 = CHCN) = (1.11 +/- 0.33) x 10(-11) and k(4)(Cl + CH2 = CHCN) = (1.11 +/- 0.23) x 1 0(-10) with uncertainties representing +/- 2 sigma. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds. (c) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码：5769 / 5777
页数：9
相关论文
共 33 条
[1]   Gas-phase OH radical-initiated oxidation of the 3-halopropenes studied by PLP-LIF in the temperature range 228-388 K [J].
Albaladejo, J ;
Ballesteros, B ;
Jiménez, E ;
de Mera, YD ;
Martínez, E .
ATMOSPHERIC ENVIRONMENT, 2003, 37 (21) :2919-2926
[2]   FIRE DEATHS IN THE GLASGOW AREA .2. THE ROLE OF CARBON-MONOXIDE [J].
ANDERSON, RA ;
WATSON, AA ;
HARLAND, WA .
MEDICINE SCIENCE AND THE LAW, 1981, 21 (04) :288-294
[3]   Low-pressure study of the reactions of Cl atoms with acrylic acid and allyl alcohol [J].
Aranda, A ;
Martínez, E ;
de Mera, YD ;
Rodríguez, A ;
Rodríguez, D ;
Cuartero, J .
ATMOSPHERIC ENVIRONMENT, 2003, 37 (31) :4361-4369
[4]   Gas-phase reaction of chlorine atoms with acrylonitrile.: Temperature and pressure dependence [J].
Aranda, A ;
de Mera, YD ;
Rodríguez, D ;
Rodríguez, A ;
Cabañas, B ;
Martínez, E .
CHEMICAL PHYSICS LETTERS, 2003, 377 (5-6) :571-576
[5]  
*ARB, 2002, CAL AIR TOX PROGR CA
[6]   Atmospheric degradation of volatile organic compounds [J].
Atkinson, R ;
Arey, J .
CHEMICAL REVIEWS, 2003, 103 (12) :4605-4638
[7]   KINETICS OF THE GAS-PHASE REACTIONS OF NO3 RADICALS WITH A SERIES OF ALKYNES, HALOALKENES, AND ALPHA,BETA-UNSATURATED ALDEHYDES [J].
ATKINSON, R ;
ASCHMANN, SM ;
GOODMAN, MA .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1987, 19 (04) :299-307
[8]   On the OH-initiated degradation of methacrylates in the troposphere: Gas-phase kinetics and formation of pyruvates [J].
Blanco, Maria B. ;
Taccone, Raul A. ;
Lane, Silvia I. ;
Teruel, Mariano A. .
CHEMICAL PHYSICS LETTERS, 2006, 429 (4-6) :389-394
[9]   Kinetics of the reactions of O(3P) with CCl2=CH2, (Z)-CHCl=CHCl, and CCl2=CCl2:: A temperature dependence study [J].
Blanco, Maria B. ;
Taccone, Raul A. ;
Lane, Silvia I. ;
Teruel, Mariano A. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (38) :11091-11097
[10]   Kinetics of reactions of chlorine atoms with a series of alkenes at 1 atm and 298 K: structure and reactivity [J].
Ezell, MJ ;
Wang, WH ;
Ezell, AA ;
Soskin, G ;
Finlayson-Pitts, BJ .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2002, 4 (23) :5813-5820
1234