Chemical Investigation on the Mechanism and Kinetics of the Atmospheric Degradation Reaction of Trichlorofluoroethene by OH⋅ and Its Subsequent Fate in the Presence of O2/NOx

Abstract

AbstractThe M06‐2X/6‐311++G(d,p) level of theory was used to examine the degradation of Trichlorofluoroethene (TCFE) initiated by OH⋅ radicals. Additionally, the coupled‐cluster single‐double with triple perturbative [CCSD(T)] method was employed to refine the single‐point energies using the complete basis set extrapolation approach. The results indicated that OH‐addition is the dominant pathway. OH⋅ adds to both the C1 and C2 carbons, resulting in the formation of the C(OH)Cl2−⋅CClF and ⋅CCl2−C(OH)ClF species. The associated barrier heights were determined to be 1.11 and −0.99 kcal mol−1, respectively. Furthermore, the energetic and thermodynamic parameters show that pathway 1 exhibits greater exothermicity and exergonicity compared to pathway 2, with differences of 8.11 and 8.21 kcal mol−1, correspondingly. The primary pathway involves OH addition to the C2 position, with a rate constant of 6.2×10−13 cm3 molecule−1 sec−1 at 298 K. This analysis served to estimate the atmospheric lifetime, along with the photochemical ozone creation potential (POCP) and ozone depletion potential (ODP). It yielded an atmospheric lifetime of 8.49 days, an ODP of 4.8×10−4, and a POCP value of 2.99, respectively. Radiative forcing efficiencies were also estimated at the M06‐2X/6‐311++G(d,p) level. Global warming potentials (GWPs) were calculated for 20, 100, and 500 years, resulting in values of 9.61, 2.61, and 0.74, respectively. TCFE is not expected to make a significant contribution to the radiative forcing of climate change. The results obtained from the time‐dependent density functional theory (TDDFT) indicated that TCFE and its energized adducts are unable to photolysis under sunlight in the UV and visible spectrum. Secondary reactions involve the [TCFE‐OH−O2]⋅ peroxy radical, leading subsequently to the [TCFE−OH−O]⋅ alkoxy radical. It was found that the alkoxy radical resulting from the peroxy radical can lead to the formation of phosgene (COCl2) and carbonyl chloride fluoride (CClFO), with phosgene being the primary product.