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Theoretical insight into OH- and Cl-initiated oxidation of CF₃OCH(CF₃)₂ and CF₃OCF₂CF₂H &fate of CF₃OC(X•)(CF₃)₂ and CF₃OCF₂CF₂X• radicals (X=O, O₂).

ABSTRACT: In this study, the mechanistic and kinetic analysis for reactions of CF₃OCH(CF₃)₂ and CF₃OCF₂CF₂H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF₃OCH(CF₃)₂/CF₃OCD(CF₃)₂ and CF₃OCF₂CF₂H/CF₃OCF₂CF₂D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF₃OC(•)(CF₃)₂ and CF₃OCF₂CF₂• in the presence of O₂ and NO. The subsequent decomposition pathways of CF₃OC(O•)(CF₃)₂ and CF₃OCF₂CF₂O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230-350?K are: k _T(1)?=?5.00?×?10^-24T^3.57 exp(-849.73/T), k _T(2)?=?1.79?×?10^-24T^4.84 exp(-4262.65/T), k_T(3)?=?1.94?×?10^-24 T^4.18 exp(-884.26/T), and k _T(4)?=?9.44?×?10^-28T^5.25 exp(-913.45/T) cm³ molecule^-1 s^-1.

SUBMITTER: Bai FY

PROVIDER: S-EPMC5220334 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature

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Publications

Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2 and CF3OCF2CF2H &fate of CF3OC(X•)(CF3)2 and CF3OCF2CF2X• radicals (X=O, O2).

Bai Feng-Yang FY Ma Yuan Y Lv Shuang S Pan Xiu-Mei XM Jia Xiu-Juan XJ

Scientific reports 20170109

In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2 and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2 and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were ...[more]

PMID: 28067283

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Project description:The OH-initiated photo-oxidation of piperidine and the photolysis of 1-nitrosopiperidine were investigated in a large atmospheric simulation chamber and in theoretical calculations based on CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The rate coefficient for the reaction of piperidine with OH radicals was determined by the relative rate method to be kOH-piperidine = (1.19 ± 0.27) × 10-10 cm3 molecule-1 s-1 at 304 ± 2 K and 1014 ± 2 hPa. Product studies show the piperidine + OH reaction to proceed via H-abstraction from both CH2 and NH groups, resulting in the formation of the corresponding imine (2,3,4,5-tetrahydropyridine) as the major product and in the nitramine (1-nitropiperidine) and nitrosamine (1-nitrosopiperidine) as minor products. Analysis of 1-nitrosopiperidine photolysis experiments under natural sunlight conditions gave the relative rates jrel = j1-nitrosoperidine/jNO2 = 0.342 ± 0.007, k3/k4a = 0.53 ± 0.05 and k2/k4a = (7.66 ± 0.18) × 10-8 that were subsequently employed in modeling the piperidine photo-oxidation experiments, from which the initial branchings between H-abstraction from the NH and CH2 groups, kN-H/ktot = 0.38 ± 0.08 and kC2-H/ktot = 0.49 ± 0.19, were derived. All photo-oxidation experiments were accompanied by particle formation that was initiated by the acid-base reaction of piperidine with nitric acid. Primary photo-oxidation products including both 1-nitrosopiperidine and 1-nitropiperidine were detected in the particles formed. Quantum chemistry calculations on the OH initiated atmospheric photo-oxidation of piperidine suggest the branching in the initial H-abstraction routes to be ∼35% N1, ∼50% C2, ∼13% C3, and ∼2% C4. The theoretical study produced an atmospheric photo-oxidation mechanism, according to which H-abstraction from the C2 position predominantly leads to 2,3,4,5-tetrahydropyridine and H-abstraction from the C3 position results in ring opening followed by a complex autoxidation, of which the first few steps are mapped in detail. H-abstraction from the C4 position is shown to result mainly in the formation of piperidin-4-one and 2,3,4,5-tetrahydropyridin-4-ol, whereas H-abstraction from N1 under atmospheric conditions primarily leads to 2,3,4,5-tetrahydropyridine and in minor amounts of 1-nitrosopiperidine and 1-nitropiperidine. The calculated rate coefficient for the piperidine + OH reaction agrees with the experimental value within 35%, and aligning the theoretical numbers to the experimental value results in k(T) = 2.46 × 10-12 × exp(486 K/T) cm3 molecule-1 s-1 (200-400 K).

Dataset Information

Theoretical insight into OH- and Cl-initiated oxidation of CF₃OCH(CF₃)₂ and CF₃OCF₂CF₂H &fate of CF₃OC(X•)(CF₃)₂ and CF₃OCF₂CF₂X• radicals (X=O, O₂).

Publications

Theoretical insight into OH- and Cl-initiated oxidation of CF<sub>3</sub>OCH(CF<sub>3</sub>)<sub>2</sub> and CF<sub>3</sub>OCF<sub>2</sub>CF<sub>2</sub>H &fate of CF<sub>3</sub>OC(X•)(CF<sub>3</sub>)<sub>2</sub> and CF<sub>3</sub>OCF<sub>2</sub>CF<sub>2</sub>X• radicals (X=O, O<sub>2</sub>).

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