Nathan A. Seifert , Branko Ruscic , Raghu Sivaramakrishnan , Kirill Prozument
{"title":"乙烯氧化过程中的C2H4O异构体","authors":"Nathan A. Seifert , Branko Ruscic , Raghu Sivaramakrishnan , Kirill Prozument","doi":"10.1016/j.jms.2023.111847","DOIUrl":null,"url":null,"abstract":"<div><p>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 SiO<sub>2</sub>/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 (CH<sub>2</sub>O), methoxy (CH<sub>3</sub>O), methanol (CH<sub>3</sub>OH), ketene (CH<sub>2</sub>CO), acetaldehyde (CH<sub>3</sub>CHO), <em>syn</em>-vinyl alcohol (<em>syn</em>-CH<sub>2</sub>CHOH), <em>anti</em>-vinyl alcohol (<em>anti</em>-CH<sub>2</sub>CHOH), oxirane (<em>c</em>-CH<sub>2</sub>OCH<sub>2</sub>), propyne (CH<sub>3</sub>CCH), and <em>syn</em>-propanal (<em>syn</em>-CH<sub>3</sub>CH<sub>2</sub>CHO). We focus on the three C<sub>2</sub>H<sub>4</sub>O species and deduce their concentration ratio [CH<sub>3</sub>CHO]:[CH<sub>2</sub>CHOH]:[<em>c</em>-CH<sub>2</sub>OCH<sub>2</sub>] = 1:0.7(2):0.06(2) by comparing the observed line intensities to those simulated with the PGOPHER software. Detailed thermochemistry of the C<sub>2</sub>H<sub>4</sub>O 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 C<sub>2</sub>H<sub>4</sub>O isomers is analyzed using a 0-D homogenous reactor kinetics simulation for ethylene oxidation. The ratios of the C<sub>2</sub>H<sub>4</sub>O isomers concentrations predicted by the kinetic model are compared to the experimental values.</p></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":1.4000,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The C2H4O isomers in the oxidation of ethylene\",\"authors\":\"Nathan A. Seifert , Branko Ruscic , Raghu Sivaramakrishnan , Kirill Prozument\",\"doi\":\"10.1016/j.jms.2023.111847\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>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 SiO<sub>2</sub>/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 (CH<sub>2</sub>O), methoxy (CH<sub>3</sub>O), methanol (CH<sub>3</sub>OH), ketene (CH<sub>2</sub>CO), acetaldehyde (CH<sub>3</sub>CHO), <em>syn</em>-vinyl alcohol (<em>syn</em>-CH<sub>2</sub>CHOH), <em>anti</em>-vinyl alcohol (<em>anti</em>-CH<sub>2</sub>CHOH), oxirane (<em>c</em>-CH<sub>2</sub>OCH<sub>2</sub>), propyne (CH<sub>3</sub>CCH), and <em>syn</em>-propanal (<em>syn</em>-CH<sub>3</sub>CH<sub>2</sub>CHO). We focus on the three C<sub>2</sub>H<sub>4</sub>O species and deduce their concentration ratio [CH<sub>3</sub>CHO]:[CH<sub>2</sub>CHOH]:[<em>c</em>-CH<sub>2</sub>OCH<sub>2</sub>] = 1:0.7(2):0.06(2) by comparing the observed line intensities to those simulated with the PGOPHER software. Detailed thermochemistry of the C<sub>2</sub>H<sub>4</sub>O 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 C<sub>2</sub>H<sub>4</sub>O isomers is analyzed using a 0-D homogenous reactor kinetics simulation for ethylene oxidation. The ratios of the C<sub>2</sub>H<sub>4</sub>O isomers concentrations predicted by the kinetic model are compared to the experimental values.</p></div>\",\"PeriodicalId\":16367,\"journal\":{\"name\":\"Journal of Molecular Spectroscopy\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2023-11-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Spectroscopy\",\"FirstCategoryId\":\"101\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022285223001121\",\"RegionNum\":4,\"RegionCategory\":\"物理与天体物理\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Spectroscopy","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022285223001121","RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL","Score":null,"Total":0}
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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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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