Relative rate (RR) technique coupled with Gas Chromatography (GC) was used to investigate the kinetics for the reactions of two hydrofluoroesters (allyl trifluoroacetate (CF3C(O)OCH2CH=CH2, ATFA) and vinyl trifluoroacetate (CF3C(O)OCH=CH2, VTFA)) with Cl atoms in between 268 and 363 K, and at 760 Torr of N2 (or air). The temperature-dependent Arrhenius expression for the title reactions were obtained to be k_(268-363 K )^(VTFA+Cl)=[(7.15±1.16)× 10^(-12) exp〖((566±50)/T)]〗 cm3 molecule-1 s-1 and k_(268-363 K )^(ATFA+Cl)=[(6.88±0.80)× 10^(-12) exp〖((794±125)/T)]〗 cm3 molecule-1 s-1 respectively. Negative temperature dependency was observed in both the title reactions. In addition to this, kinetics for the studied reactions were evaluated computationally at CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level of theory in the temperature range of 200-400 K using Canonical Variational Transition State theory (CVT) in conjunction with Small Curvature Tunneling (SCT) corrections and Interpolated Single Point Energy (ISPE) methods. Also, the products analysis for the reactions of VTFA and ATFA with Cl atoms in the presence of O2 were investigated using Gas Chromatography with Mass Spectrometer (GC-MS) and Gas Chromatography with Infrared spectroscopy (GC-IR). The plausible oxidation mechanism for the title reactions were proposed based on the product analyses. Further to comprehend the impact of these molecules on the Earth’s troposphere, atmospheric lifetimes, lifetime-corrected Radiative forcing (RFs) and Global Warming potential (GWPs) were estimated and presented in this manuscript. “Cl Atom Initiated Photo-Oxidation Reactions of Vinyl Trifluoroacetate and Allyl Trifluoroacetate in the Tropospheric Conditions”
R. Kaipara & B. Rajakumar. J. Phys. Chem. A. 2020, 124 (11), 2123-2139.
Relative rate (RR) technique coupled with Gas Chromatography (GC) was used to investigate the kinetics for the reactions of two hydrofluoroesters (allyl trifluoroacetate (CF3C(O)OCH2CH=CH2, ATFA) and vinyl trifluoroacetate (CF3C(O)OCH=CH2, VTFA)) with Cl atoms in between 268 and 363 K, and at 760 Torr of N2 (or air). The temperature-dependent Arrhenius expression for the title reactions were obtained to be k_(268-363 K )^(VTFA+Cl)=[(7.15±1.16)× 10^(-12) exp〖((566±50)/T)]〗 cm3 molecule-1 s-1 and k_(268-363 K )^(ATFA+Cl)=[(6.88±0.80)× 10^(-12) exp〖((794±125)/T)]〗 cm3 molecule-1 s-1 respectively. Negative temperature dependency was observed in both the title reactions. In addition to this, kinetics for the studied reactions were evaluated computationally at CCSD(T)/cc-pVTZ//MP2/6-311++G(d,p) level of theory in the temperature range of 200-400 K using Canonical Variational Transition State theory (CVT) in conjunction with Small Curvature Tunneling (SCT) corrections and Interpolated Single Point Energy (ISPE) methods. Also, the products analysis for the reactions of VTFA and ATFA with Cl atoms in the presence of O2 were investigated using Gas Chromatography with Mass Spectrometer (GC-MS) and Gas Chromatography with Infrared spectroscopy (GC-IR). The plausible oxidation mechanism for the title reactions were proposed based on the product analyses. Further to comprehend the impact of these molecules on the Earth’s troposphere, atmospheric lifetimes, lifetime-corrected Radiative forcing (RFs) and Global Warming potential (GWPs) were estimated and presented in this manuscript.