Kumar Avinash, Mondal Koushik, Rajakumar B
Department of Chemistry, Indian Institute of Technology Madras, Chennai600036, India.
Center for Atmospheric and Climate Sciences, Indian Institute of Technology Madras, Chennai600036, India.
J Phys Chem A. 2021 Oct 14;125(40):8869-8881. doi: 10.1021/acs.jpca.1c06590. Epub 2021 Sep 29.
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 cm molecule s, and the Arrhenius expression was derived to be = (1.61 ± 0.35) × 10 exp{(1256 ± 236)/T} cm molecule s. 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 = (1.59 ± 0.35) × 10exp{(1389 ± 62)/T} cm molecule s. 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.
采用脉冲激光光解-激光诱导荧光（PLP-LIF）技术，在278 - 363 K的温度范围内通过实验测定了2-乙氧基乙醇与羟基自由基的反应活性。室温下测得的速率系数为(1.14 ± 0.03) × 10 cm³分子⁻¹ s⁻¹，得到的阿伦尼乌斯表达式为 = (1.61 ± 0.35) × 10¹² exp{(1256 ± 236)/T} cm³分子⁻¹ s⁻¹。使用在CCSD(T)/aug-cc-pVTZ//M06-2X/6-31+G(d,p)理论水平上结合隧道效应校正的先进方法，在200 - 400 K的温度范围内对该标题反应的动力学进行了计算。从计算得到的速率系数得出的阿伦尼乌斯表达式为 = (1.59 ± 0.35) × 10¹² exp{(1389 ± 62)/T} cm³分子⁻¹ s⁻¹。还利用计算得到的热化学参数确定了各反应途径的可行性。本文计算并讨论了诸如累积大气寿命和光化学臭氧生成潜力等大气影响参数。
