在对流层相关条件下对戊酸甲酯和异戊酸甲酯进行的氯引发光氧化研究。
Cl-Initiated Photo-oxidation Studies of Methyl Valerate and Methyl Isovalerate under Tropospherically Relevant Conditions.
作者信息
Kaipara Revathy, Rajakumar B
机构信息
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
出版信息
J Phys Chem A. 2020 Apr 2;124(13):2515-2529. doi: 10.1021/acs.jpca.9b10740. Epub 2020 Mar 23.
Rate coefficients for the reactions of methyl valerate (MV) and methyl isovalerate (MIV) were investigated using the relative rate (RR) technique in the temperature range of 268-363 K and at 760 Torr of N. The rate coefficients at 298 ± 2 K were measured to be = (1.69 ± 0.40) × 10 cm molecule s and = (1.06 ± 0.23) × 10 cm molecule s. To comprehend the experimentally measured rate coefficients, kinetic parameters for the title reactions were computed at the CCSD(T)/cc-pVTZ//BHandHLYP/6-311+G(d,p) level of theory over the temperature range of 200-400 K using canonical variational transition (CVT) state theory in conjunction with small curvature tunneling (SCT) corrections and the interpolated single-point energy (ISPE) method. Additionally, the degradation mechanisms were proposed based on the analyzed products. Moreover, to further understand the atmospheric fate of these molecules in the troposphere, atmospheric lifetimes, radiative forcings (RFs), and global warming potentials (GWPs) were calculated.
在268 - 363 K的温度范围内以及760 Torr的氮气环境下，采用相对速率（RR）技术研究了戊酸甲酯（MV）和异戊酸甲酯（MIV）反应的速率系数。在298 ± 2 K时测得的速率系数分别为 = (1.69 ± 0.40) × 10 cm³分子⁻¹ s⁻¹和 = (1.06 ± 0.23) × 10 cm³分子⁻¹ s⁻¹。为了理解实验测得的速率系数，使用正则变分过渡（CVT）态理论结合小曲率隧道效应（SCT）校正和内插单点能量（ISPE）方法，在CCSD(T)/cc-pVTZ//BHandHLYP/6-311+G(d,p)理论水平上，计算了200 - 400 K温度范围内标题反应的动力学参数。此外，基于分析的产物提出了降解机制。此外，为了进一步了解这些分子在对流层中的大气归宿，计算了大气寿命、辐射强迫（RFs）和全球变暖潜能值（GWPs）。
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