Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure |
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| Authors: | María B Blanco Iustinian Bejan Ian Barnes Peter Wiesen Mariano A Teruel |
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| Institution: | 1. Instituto de Investigaciones en Fisicoquímica, I.N.F.I.Q.C., Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina;2. Physikalische Chemie/FBC, Bergische Universitaet Wuppertal, Wuppertal, Germany;1. Politecnico di Milano, Dipartimento di Energia, Piazza Leonardo da Vinci 32, 20133 Milano, Italy;2. Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria Chimica, Piazza Leonardo da Vinci 32, 20133 Milano, Italy;1. Computational Chemistry Research Group, Ton Duc Thang University, Ho Chi Minh City, Viet Nam;2. Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Viet Nam;3. Department of Applied Chemistry and Institute of Natural Sciences, Kyung Hee University, Gyeonggi-do 446-701, South Korea;4. Faculty of Chemistry, University of Science, Vietnam National University, Ho Chi Minh City, Viet Nam;5. New Industry Creation Hatchery Center, Tohoku University, Sendai 980-8579, Japan;6. Theory and Modeling Department, Culham Centre for Fusion Energy, United Kingdom Atomic Energy Authority, Abingdon OX14 3DB, United Kingdom;1. Science and Technology on Plasma Physics Laboratory, Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900, PR China;2. National Synchrotron Radiation Laboratory, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, Anhui 230029, PR China;3. Institute of Chemical Material, China Academy of Engineering Physics, Mianyang 621900, PR China;1. School of Computer Science and Engineering, International University, VNU-HCM, Quarter 6, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Vietnam;2. School of Biotechnology, International University, VNU-HCM, Quarter 6, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Vietnam |
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| Abstract: | Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH2 C(CH3)C(O)OCH3 (MMA), CH2CHC(O)OCH3 (MAC) and CH2C(CH3)C(O)O(CH2)3CH3 (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10?10 cm3 molecule?1 s?1) as follows: k(Cl+MMA) = 2.82 ± 0.93, k(Cl+MAC) = 2.04 ± 0.54 and k(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm3 molecule?1 s?1): k(Cl+MMA) = (13.9 ± 7.8) × 10?15 exp(2904 ± 420)/T], k(Cl+MAC) = (0.4 ± 0.2) × 10?15 exp(3884 ± 879)/T], k(Cl+BMA) = (0.98 ± 0.42) × 10?15 exp(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log kOH = 1.09 log kCl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed. |
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