An experimental and theoretical study of photo-oxidation reaction of 2-methyl tetrahydrofuran with Cl atom under atmospheric conditions.

Autor: Nayak, Subhadarsi, Joy, Fredy, Rajakumar, Balla
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Zdroj: Environmental Science & Pollution Research; Aug2024, Vol. 31 Issue 39, p51473-51488, 16p
Abstrakt: Temperature-dependent rate coefficients for the reactions of 2-methyl tetrahydrofuran (MTHF) with Cl atoms in the temperature range of 268–343 K at atmospheric pressure were measured using the relative-rate method. Ethylene and propane were used as reference compounds. Quantitative analysis of the post-photolysis reaction mixture was conducted using a gas chromatograph paired with a flame ionization detector (GC-FID). A gas chromatograph connected to a mass spectrometer (GC–MS) was employed for the purpose of qualitative analysis. In the experimental temperature range, the derived Arrhenius expression for the title reaction is represented by the equation k M T H F + C l Expt 268 - 343 K = (1.48 ± 0.13) × 10 - 12 × e x p 1474.51 ± 25.16 T cm3 molecule−1 s−1. In addition to our experimental findings, we conducted computational calculations employing the CCSD(T)//BHandHLYP/6–31 + G(d,p) level of theory to complement our study. The canonical transition state theory (CTST) was utilized to compute the rate coefficients at 250–400 K and 760 Torr. The Arrhenius expression for the theoretically calculated "k" values is found to be k M T H F + C l Theory 250 - 400 K = (1.51 ± 0.10) × 10 - 12 × e x p 1544.97 ± 22.14 T cm3 molecule−1 s−1. The local reactivity parameters, such as Fukui functions ( f r 0 ), local softness ( s r 0 ), and global softness (S ) were also calculated theoretically to understand the site-specific reactivity trend of MTHF towards Cl atoms. The atmospheric implications, branching ratios, degradation mechanism, and feasibility of the reaction are discussed in this study. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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