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DOI10.1039/c3cp52851k
A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides
Piletic, Ivan R.1; Edney, Edward O.1; Bartolotti, Libero J.2
发表日期2013
ISSN1463-9076
卷号15期号:41页码:18065-18076
英文摘要

Epoxides are important intermediates of atmospheric isoprene oxidation. Their subsequent reactions in the particle phase lead to the production of organic compounds detected in ambient aerosols. We apply density functional theory to determine the important kinetic factors that drive epoxide reactions in the particle phase. Specifically, the importance of acid catalysis and solvent polarity are investigated using a variety of epoxides and nucleophiles. The condensed phase is modeled using molecular clusters immersed in a dielectric continuum and a majority of the calculations are performed with the M062x density functional and the 6-311++G** basis set. Calculations of acid catalyzed epoxide hydrolysis transition states for simple primary, secondary and tertiary epoxides are consistent with an A-2 mechanism where the nucleophile (water) interacts with an epoxide carbon in the transition state. By applying transition state theory to this mechanism, the overall rate constants of epoxide reactions such as hydrolysis, organosulfate formation, organonitrate formation and oligomerization are determined. The calculations indicate that the acid catalyzed hydrolysis rate constant of 2-methyl-2,3-epoxybutane-1,4- diol (beta-IEPOX - an isoprene epoxide produced under low NOx conditions) is approximately 30 times greater than 2-methyl-2,3-epoxypropanoic acid (MAE - methacrylic acid epoxide derived from isoprene and produced at high NOx concentrations). Furthermore, acid catalyzed organosulfate formation and epoxide oligomerization reactions are competitive and appear to be kinetically favorable over the hydrolysis of IEPOX.


语种英语
WOS记录号WOS:000325400600040
来源期刊PHYSICAL CHEMISTRY CHEMICAL PHYSICS
来源机构美国环保署
文献类型期刊论文
条目标识符http://gcip.llas.ac.cn/handle/2XKMVOVA/58831
作者单位1.US EPA, Natl Exposure Res Lab, Res Triangle Pk, NC 27711 USA;
2.E Carolina Univ, Dept Chem, Greenville, NC 27858 USA
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Piletic, Ivan R.,Edney, Edward O.,Bartolotti, Libero J.. A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides[J]. 美国环保署,2013,15(41):18065-18076.
APA Piletic, Ivan R.,Edney, Edward O.,&Bartolotti, Libero J..(2013).A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,15(41),18065-18076.
MLA Piletic, Ivan R.,et al."A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 15.41(2013):18065-18076.
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