کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5752854 | 1620308 | 2017 | 35 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Experimental and theoretical investigations of the kinetics and mechanism of the Cl + 4-hydroxy-4-methyl-2-pentanone reaction
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
علوم زمین و سیارات
علم هواشناسی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
The reaction of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) with Cl atoms was studied for the first time experimentally and theoretically. Relative kinetic measurements were carried out at room temperature and 1 bar of synthetic air/N2 in two different environmental chambers: a 300 L Teflon bag and a 16 L borosilicate glass cell. Reactants, reference compounds and products were monitored either by IR absorption or by GC-FID. Theoretical calculations were performed using the density functional theory method at BH&HLYP level of theory for twelve hydrogen abstraction pathways. The individual rate coefficients for the most favorable H-abstraction pathways were calculated by canonical variational theory using small curvature tunneling method at 298 K. An average experimental rate coefficient of (7.4 ± 0.6) Ã 10â11 cm3 moleculeâ1 sâ1 was obtained at 298 K, in good agreement with the theoretical rate coefficient. The branching ratios for each reaction channel were evaluated theoretically from the individual rate coefficients of the identified channels. The H-atom abstracted on the -CH2 group appeared to be the dominant channel with a small barrier height. Formaldehyde, acetic acid, HCl, CO2 and CO were identified by IR as the major primary products. The obtained results are presented and discussed in terms of structure-reactivity relationships. A mechanism is suggested for the formation of the observed products. The atmospheric implications of the studied reaction are presented and more particularly, the lifetime of 4H4M2P towards Cl atoms is evaluated to be about 3 days.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Atmospheric Environment - Volume 166, October 2017, Pages 315-326
Journal: Atmospheric Environment - Volume 166, October 2017, Pages 315-326
نویسندگان
L. Aslan, A. Mano Priya, C. Sleiman, M.N. Zeineddine, P. Coddeville, C. Fittschen, B. Ballesteros, A. Canosa, L. Senthilkumar, G. El Dib, A. Tomas,