Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase |
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| Institution: | 1. Department of Physics, Laboratory for Thin Films Nanosystems and Nanometrology – LTFN, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece;2. Department of Physics, National Technical University of Athens, GR-15780 Athens, Greece;1. College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China;2. Guangdong Provincial Environmental Monitoring Center, Guangzhou 510045, China;1. Centro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal;2. Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250, USA;1. Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 510640, Guangzhou, China;2. Department of Chemistry, University of California, Irvine, CA, USA;1. School of Physics, Georgia Institute of Technology, Atlanta, GA 30332, USA;2. School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332 USA;1. Department of Psychology, East Tennessee State University, Johnson City, TN 37614, United States;2. Department of Biomedical Sciences, James H. Quillen College of Medicine, East Tennessee State University, Johnson City, TN 37614, United States;3. Department of Psychology, St. Norbert College, De Pere, WI, 54115,United States;4. Department of Pharmaceutical Sciences, College of Pharmacy, University of Kentucky, Lexington, KY 40536, United States |
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| Abstract: | 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 cm3 molecule−1 s−1): k1(OH+CH2 CHC(O)OH)=(1.75±0.47)×10−11, k2(Cl+CH2CHC(O)OH)=(3.99±0.84)×10−10, k3(OH+CH2CHCN)=(1.11±0.33)×10−11 and k4(Cl+CH2CHCN)=(1.11±0.23)×10−10 with uncertainties representing ±2σ. 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. |
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