A Combined Experimental and Theoretical Study to Determine the Kinetics of 2-Ethoxy Ethanol with OH Radical in the Gas Phase

Abstract

The reactivity of 2-ethoxy ethanol with OH radicals was experimentally measured in the temperature range of 278−363 K using the pulsed laser photolysis−laser-induced fluorescence (PLP−LIF) technique. The rate coefficient at room temperature was measured to be (1.14 ± 0.03) × 10 −11 cm 3 molecule −1 s −1 , and the Arrhenius expression was derived to be k expt 278−363K = (1.61 ± 0.35) × 10 −13 exp{(1256 ± 236)/T} cm 3 molecule −1 s −1 . Computational calculations were performed to compute the kinetics of the titled reaction in the temperature range of 200− 400 K using advanced methods incorporated with tunneling correction at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-31+G(d,p) level of theory. The Arrhenius expression derived from the computationally calculated rate coefficients is k theo 200−400K = (1.59 ± 0.35) × 10 −13 exp{(1389 ± 62)/T} cm 3 molecule −1 s −1 . The feasibility of each reaction pathway was also determined using the calculated thermochemical parameters. Atmospheric implication parameters such as cumulative atmospheric lifetime and photochemical ozone creation potential were calculated and are discussed in this paper.

Photo-oxidation reaction of tert-butyl chloride with OH radicals and Cl atoms in the troposphere and its implications

“…The schematic diagram and in-detail description of the PLP-LIF experimental setup are given in a previous publication, and only the essential details are briefly described here. 11 The experiment was conducted in a double-jacketed Pyrex glass cell (internal volume B200 cm 3 ). Fused silica windows (Thorlabs) were attached to the entrances and exits for the photolysis and probe beams and kept at Brewster's angle to the incident beams to maximize transmission and minimize window scattering.…”

CH3O Substitution Effect Revisited in the Vibrationally Resolved Laser-Induced Fluorescence Spectra of Methoxycyclohexoxy Radicals

“…7 Structure− activity relationship associated with alkoxy reaction barrier heights and reaction pathway competition was further investigated and discussed by Orlando, 9 Vereecken, 10,11 Carrasquillo, 12 and other researchers. 13 It is recognized that the fate of alkoxy radicals strongly depends on the structure and substitution, especially in hydroxyalkoxy radicals, oxysubstituted alkoxy radicals, and halogenated alkoxy radicals. 14−16 In recent years, experimental and theoretical investigations of hydroxy-substituted and halogenated alkoxy radicals have been reported.…”

“…Alkoxy radicals have been extensively studied due to their significance in ozone chemistry. − They are intermediate products produced during the oxidation of organic compounds in the presence of nitrogen oxides (NO x ). − The competition between the three reaction pathways of alkoxy radicals in the atmosphere, i.e., isomerization, β C–C bond scission, and reaction with O 2 , may result in large uncertainties in the rate of ozone production. ,, In 1997, Atkinson proposed an estimation method for the calculation of alkoxy reaction rates in the troposphere on the basis of the experimental observation that the alkyl leaving group influenced the energetics of the alkoxy radical decomposition . Structure–activity relationship associated with alkoxy reaction barrier heights and reaction pathway competition was further investigated and discussed by Orlando, Vereecken, , Carrasquillo, and other researchers . It is recognized that the fate of alkoxy radicals strongly depends on the structure and substitution, especially in hydroxyalkoxy radicals, oxy-substituted alkoxy radicals, and halogenated alkoxy radicals. − …”