乙烯氧化过程中的C2H4O异构体

IF 1.4 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
Nathan A. Seifert , Branko Ruscic , Raghu Sivaramakrishnan , Kirill Prozument
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引用次数: 0

摘要

结合旋转光谱,热化学和动力学建模研究探索乙醛(乙醛),乙烯醇(乙醇)和环氧乙烷(氧环烷)在乙烯(乙烯)氧化过程中的形成机制。利用BrightSpec w波段啁啾脉冲傅立叶变换毫米波光谱仪对1700 K下SiO2/SiC微反应器中氧化中间体和产物进行了多路定量检测。宽带旋转光谱包含甲醛(CH2O)、甲氧基(ch30)、甲醇(CH3OH)、烯酮(CH2CO)、乙醛(CH3CHO)、正乙烯醇(syn-CH2CHOH)、反乙烯醇(anti-CH2CHOH)、氧烷(c-CH2OCH2)、丙炔(CH3CCH)和正丙烷(syn-CH3CH2CHO)的跃迁。以三种c2h40o为研究对象,通过与PGOPHER软件模拟的线强度对比,推导出它们的浓度比[CH3CHO]:[CH2CHOH]:[c-CH2OCH2] = 1:7 .7(2):0.06(2)。c2h40o异构体和构象的详细热化学性质由活性热化学表提供。与1700 K(1:0. 07:0.000024)的平衡比相比,观察到乙醛和氧环烷相对于更稳定的乙醛的过量浓度,指出了这些高能量异构体的直接化学途径。采用0-D均相反应器模拟乙烯氧化反应,分析了三种c2h40o异构体的形成机理。将动力学模型预测的c2h40o同分异构体浓度与实验值进行了比较。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

The C2H4O isomers in the oxidation of ethylene

The C2H4O isomers in the oxidation of ethylene

A combined rotational spectroscopy, thermochemistry, and kinetic modeling study explores the mechanism of acetaldehyde (ethanal), vinyl alcohol (ethenol), and ethylene oxide (oxirane) formation in the oxidation of ethylene (ethene). Multiplexed quantitative detection of oxidation intermediates and products exiting a SiO2/SiC microreactor at 1700 K is demonstrated with the BrightSpec W-band chirped-pulse Fourier transform millimeter-wave spectrometer. The broadband rotational spectrum contains transitions of formaldehyde (CH2O), methoxy (CH3O), methanol (CH3OH), ketene (CH2CO), acetaldehyde (CH3CHO), syn-vinyl alcohol (syn-CH2CHOH), anti-vinyl alcohol (anti-CH2CHOH), oxirane (c-CH2OCH2), propyne (CH3CCH), and syn-propanal (syn-CH3CH2CHO). We focus on the three C2H4O species and deduce their concentration ratio [CH3CHO]:[CH2CHOH]:[c-CH2OCH2] = 1:0.7(2):0.06(2) by comparing the observed line intensities to those simulated with the PGOPHER software. Detailed thermochemistry of the C2H4O isomers and conformers is provided by Active Thermochemical Tables. The observed excess concentrations of vinyl alcohol and oxirane relative to the more stable acetaldehyde compared to the equilibrium ratio at 1700 K (1:0.087:0.000024), point to direct chemical pathways to these higher energy isomers. The mechanism for the formation of the three C2H4O isomers is analyzed using a 0-D homogenous reactor kinetics simulation for ethylene oxidation. The ratios of the C2H4O isomers concentrations predicted by the kinetic model are compared to the experimental values.

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来源期刊
CiteScore
2.70
自引率
21.40%
发文量
94
审稿时长
29 days
期刊介绍: The Journal of Molecular Spectroscopy presents experimental and theoretical articles on all subjects relevant to molecular spectroscopy and its modern applications. An international medium for the publication of some of the most significant research in the field, the Journal of Molecular Spectroscopy is an invaluable resource for astrophysicists, chemists, physicists, engineers, and others involved in molecular spectroscopy research and practice.
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