Artículo
Atmospheric chemistry of trifluorodicarbonyls initiated by Cl atoms: Reactivity trends, mechanism, and acid formation yields
Lugo Garcia, Pedro Luis
; Straccia Cepeda, Vianni Giovanna
; Rivela Fretes, Cynthia Beatriz
; Teruel, Mariano Andres
; Blanco, Maria Belen





Fecha de publicación:
03/2024
Editorial:
Elsevier
Revista:
Journal of Environmental Sciences
ISSN:
1001-0742
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Rate coefficients of the gas-phase reactions of Cl atoms with a series of fluorinated diketones (FDKs): CF3C(O)CH2C(O)CH3 (TFP), CF3C(O)CH2C(O)CH2CH3 (TFH) and CF3C(O)CH2C(O)CH(CH3)2 (TFMH), have been measured at (298 ± 2) K and under atmospheric pressure. The experiments were performed using the relative-rate method with a GC-FID detection system. From different determinations and references used, the following rate coefficients were obtained (in cm3/(molecule·sec)): k4(TFP + Cl) = (1.75 ± 0.21) × 10−10, k5(TFH + Cl) = (2.05 ± 0.23) × 10−10, k6(TFMH + Cl) = (2.71 ± 0.34) × 10−10. Reactivity trends of FDKs were discussed and Free Energy Relationships analysis was developed. The expression lgkOH = 1.68 lgkCl + 5.71 was obtained for the reactivity of the studied FDKs together with similar unsaturated VOCs with Cl and OH radicals Additionally, acetic acid (CH3C(O)OH) and trifluoroacetic acid (CF3C(O)OH) were positively identified and quantified as degradation products using in situ FTIR spectroscopy. According to the identified products, atmospheric chemical mechanisms were proposed. The atmospheric implications of the studied reactions were assessed by the estimation of the tropospheric lifetimes of TFP, TFH, and TFMH concerning their reaction with Cl atoms to be 48, 41, and 31 hours, respectively.The relatively short residence in the atmosphere of the fluorocarbons studied will have a local/regional impact with restricted transport. Global warming potential (GWP(20 yr)) calculated for the studied fluoro diketones were 0.014, 0.003 and 0.001 for TFP, TFH and TFMH, respectively with a negligible contribution to the greenhouse effect.
Palabras clave:
KINETICS
,
CL-INITIATED
,
DEGRADATION
,
FLUOROIKETONES
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Identificadores
Colecciones
Articulos(CIBICI)
Articulos de CENTRO DE INV.EN BIOQUI.CLINICA E INMUNOLOGIA
Articulos de CENTRO DE INV.EN BIOQUI.CLINICA E INMUNOLOGIA
Articulos(INFIQC)
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Articulos de INST.DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Citación
Lugo Garcia, Pedro Luis; Straccia Cepeda, Vianni Giovanna; Rivela Fretes, Cynthia Beatriz; Teruel, Mariano Andres; Blanco, Maria Belen; Atmospheric chemistry of trifluorodicarbonyls initiated by Cl atoms: Reactivity trends, mechanism, and acid formation yields; Elsevier; Journal of Environmental Sciences; 151; 3-2024; 12-25
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