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

Guido N Rimondino; Walter J Peláez; Fabio E Malanca

doi:10.1021/acs.jpca.9b09887

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

J Phys Chem A. 2020 Jan 9;124(1):56-62. doi: 10.1021/acs.jpca.9b09887. Epub 2019 Dec 18.

Authors

Guido N Rimondino¹, Walter J Peláez¹, Fabio E Malanca¹

Affiliation

¹ INFIQC - CONICET - Instituto de Investigaciones en Fisicoquímica de Córdoba, Departamento de Fisicoquímica, Facultad de Ciencias Químicas , Universidad Nacional de Córdoba , Ciudad Universitaria (X5000HUA) , Córdoba , República Argentina.

PMID: 31800246
DOI: 10.1021/acs.jpca.9b09887

Abstract

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 cm³ 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 CH₃CH₂OC(O)OCHO, CH₃CH₂OC(O)OCH₂CHO, CH₃CH₂OC(O)OC(O)CH₃, CO₂, CO, HCOOH, and CH₃COOH. 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 photo-oxidation and the identity of CH₃CH₂OC(O)OCHO, CH₃CH₂OC(O)OC(O)CH₃, and CH₃CH₂OC(O)OCH₂CHO 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.