Atmospheric degradation of n -butyl formate in the presence of O 2 and NO 2

Vila, Jesús Alberto; Argüello, Gustavo A.; Malanca, Fabio Ernesto

doi:10.1016/j.jphotochem.2018.04.052

Cited by 2 publications

(4 citation statements)

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“…Considering the values presented above, the rate coefficient for DEC can be estimated as 1.08 × 10 –11 cm 3 molecule –1 s –1 , showing an excellent concordance with the experimental value obtained in this work. This result also corroborates the value of the F (−CH 2 OC(O)) factor obtained by Vila et al for the study of the gas-phase degradation of n -butyl formate …”

Section: Resultssupporting

confidence: 91%

“…Value for F(-OC(O)O) = 0.035 was derived from the attack of chlorine atoms on dimethyl carbonate, according to the experimental rate coefficient measured by Bilde et al20 Considering the values presented above, the rate coefficient for DEC can be estimated as 1.08 × 10 −11 cm 3 molec −1 s −1 , showing an excellent concordance with the experimental value obtained in this work. This result also corroborates the value of the F(-CH 2 OC(O)) factor obtained by Vila et al for the study of the gas phase degradation of nbutyl formate 19.…”

supporting

confidence: 91%

“…This result also corroborates the value of the F(−CH 2 OC(O)) factor obtained by Vila et al for the study of the gas-phase degradation of n-butyl formate. 19 From the SAR method, the relative reactivity trend for each hydrogen atom in the molecule can also be estimated. For instance, two possible attack positions are available at DEC moiety: the abstraction of an H atom from the −CH 2 − groups and the corresponding one to −CH 3 groups, herein named "via α" and "via β", respectively, according to their position with regard to the carbonate moiety.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…allows the calculation of the rate coefficients of organic molecules based on the estimation of methyl, methylene, and methine group rate constants (k prim , k sec , and k tert , respectively) and parameters (F) associated to the functional groups bonded to each one. The values available in bibliography for these mathematical terms are: k prim = 3.32 x 10 -11 cm 3 molecule -1 s -1 , k sec = 8.34 x 10 -11 cm 3 molecule -1 s -1 , F(-CH 3 ) = 1.00, F(-CH 2 -) = 0.79, and F(-CH 2 OC(O)) = 0.075 19. Value for F(-OC(O)O) = 0.035 was derived from the attack of chlorine atoms on dimethyl carbonate, according to the experimental rate coefficient measured by Bilde et al20 Considering the values presented above, the rate coefficient for DEC can be estimated as 1.08 × 10 −11 cm 3 molec −1 s −1 , showing an excellent concordance with the experimental value obtained in this work.…”

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Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism

2019

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The rate coefficient for the gas-phase of diethyl carbonate with chlorine atoms has been determined at 298 K using a relative method, employing ethyl formate and ethyl acetate as reference compounds. The experimental value, (1.0 ± 0.2) × 10 −11 cm 3 molecule -1 s -1 , is in good correlation with the one estimated by the SAR (Structure-Activity Relationship) method. The photo-oxidation mechanism of diethyl carbonate initiated by chlorine atoms was also studied at 298 K and atmospheric pressure as a function of the oxygen partial pressure. The main products identified by infrared spectroscopy were: CH 3 CH 2 OC(O)OCHO, CH 3 CH 2 OC(O)OCH 2 CHO, CH 3 CH 2 OC(O)OC(O)CH 3 , CO 2 , CO, HCOOH, and CH 3 COOH. The results reveal that the oxidation process occurs by the abstraction of a hydrogen atom from the methyl (43%) and methylene (57%) groups. The relative importance of each reaction path from the primary radicals formed in photooxidation and the identity of CH 3 CH 2 OC(O)OCHO, CH 3 CH 2 OC(O)OC(O)CH 3, and CH 3 CH 2 OC(O)OCH 2 CHO were determined using computational methods. The activation energy of reaction paths for the main oxygenated radicals formed during photo-oxidation was determined using Gaussian09 Program.

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Section: Resultssupporting

confidence: 91%

supporting

confidence: 91%

Section: ■ Results and Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

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