Binod Raj Giri, Tam V.-T. Mai, Krishna Prasad Shrestha, Sushant Giri, R. Thirumaleswara Naik, Rakhi Verma, Fabian Mauss, Lam K. Huynh
{"title":"NH2与二甲醚和乙醚反应的理论动力学研究:动力学模型的意义","authors":"Binod Raj Giri, Tam V.-T. Mai, Krishna Prasad Shrestha, Sushant Giri, R. Thirumaleswara Naik, Rakhi Verma, Fabian Mauss, Lam K. Huynh","doi":"10.1002/kin.21779","DOIUrl":null,"url":null,"abstract":"<p>Ammonia (NH<sub>3</sub>) and hydrogen (H<sub>2</sub>) have emerged as promising carbon-free fuels to help mitigate global warming by reducing greenhouse gas emissions. Our ongoing research currently focuses on understanding the combustion characteristics of NH<sub>3</sub> blends with oxygenates and hydrocarbons, uncovering the critical role of carbon–nitrogen cross-reactions in accurately modeling their combustion behavior. Amino (NH<sub>2</sub>) radicals, which are abundant in ammonia and nitrogen-rich environments, strongly influence the low-temperature reactivity of NH<sub>3</sub>-hydrocarbon/oxygenate mixtures, affecting overall reactivity and emission characteristics. Recognizing the importance of NH<sub>2</sub> radicals, we investigated the reaction kinetics of NH<sub>2</sub> with dimethyl ether (DME, CH<sub>3</sub>OCH<sub>3</sub>) and diethyl ether (DEE, CH<sub>3</sub>CH<sub>2</sub>OCH<sub>2</sub>CH<sub>3</sub>) using appropriate high-level ab initio and statistical rate theory methods. We computed the potential energy profiles at the CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory, analyzing the reactivity of NH<sub>2</sub> radicals at various C─H sites of these diethers. Incorporating these newly derived rate parameters, our updated kinetic model successfully captures previous experimental data, addressing the modeling challenges encountered in our earlier studies. Our findings, including insights into the impact of NH<sub>2</sub> radicals, contribute to an understanding of ammonia combustion and its potential in achieving carbon-neutral energy systems.</p>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 6","pages":"353-363"},"PeriodicalIF":1.5000,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/kin.21779","citationCount":"0","resultStr":"{\"title\":\"Theoretical Kinetic Study of NH2 Reactions With Dimethyl Ether and Diethyl Ether: Implications for Kinetic Modeling\",\"authors\":\"Binod Raj Giri, Tam V.-T. Mai, Krishna Prasad Shrestha, Sushant Giri, R. Thirumaleswara Naik, Rakhi Verma, Fabian Mauss, Lam K. Huynh\",\"doi\":\"10.1002/kin.21779\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Ammonia (NH<sub>3</sub>) and hydrogen (H<sub>2</sub>) have emerged as promising carbon-free fuels to help mitigate global warming by reducing greenhouse gas emissions. Our ongoing research currently focuses on understanding the combustion characteristics of NH<sub>3</sub> blends with oxygenates and hydrocarbons, uncovering the critical role of carbon–nitrogen cross-reactions in accurately modeling their combustion behavior. Amino (NH<sub>2</sub>) radicals, which are abundant in ammonia and nitrogen-rich environments, strongly influence the low-temperature reactivity of NH<sub>3</sub>-hydrocarbon/oxygenate mixtures, affecting overall reactivity and emission characteristics. Recognizing the importance of NH<sub>2</sub> radicals, we investigated the reaction kinetics of NH<sub>2</sub> with dimethyl ether (DME, CH<sub>3</sub>OCH<sub>3</sub>) and diethyl ether (DEE, CH<sub>3</sub>CH<sub>2</sub>OCH<sub>2</sub>CH<sub>3</sub>) using appropriate high-level ab initio and statistical rate theory methods. We computed the potential energy profiles at the CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory, analyzing the reactivity of NH<sub>2</sub> radicals at various C─H sites of these diethers. Incorporating these newly derived rate parameters, our updated kinetic model successfully captures previous experimental data, addressing the modeling challenges encountered in our earlier studies. Our findings, including insights into the impact of NH<sub>2</sub> radicals, contribute to an understanding of ammonia combustion and its potential in achieving carbon-neutral energy systems.</p>\",\"PeriodicalId\":13894,\"journal\":{\"name\":\"International Journal of Chemical Kinetics\",\"volume\":\"57 6\",\"pages\":\"353-363\"},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2025-01-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/kin.21779\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Chemical Kinetics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/kin.21779\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Chemical Kinetics","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/kin.21779","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Theoretical Kinetic Study of NH2 Reactions With Dimethyl Ether and Diethyl Ether: Implications for Kinetic Modeling
Ammonia (NH3) and hydrogen (H2) have emerged as promising carbon-free fuels to help mitigate global warming by reducing greenhouse gas emissions. Our ongoing research currently focuses on understanding the combustion characteristics of NH3 blends with oxygenates and hydrocarbons, uncovering the critical role of carbon–nitrogen cross-reactions in accurately modeling their combustion behavior. Amino (NH2) radicals, which are abundant in ammonia and nitrogen-rich environments, strongly influence the low-temperature reactivity of NH3-hydrocarbon/oxygenate mixtures, affecting overall reactivity and emission characteristics. Recognizing the importance of NH2 radicals, we investigated the reaction kinetics of NH2 with dimethyl ether (DME, CH3OCH3) and diethyl ether (DEE, CH3CH2OCH2CH3) using appropriate high-level ab initio and statistical rate theory methods. We computed the potential energy profiles at the CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory, analyzing the reactivity of NH2 radicals at various C─H sites of these diethers. Incorporating these newly derived rate parameters, our updated kinetic model successfully captures previous experimental data, addressing the modeling challenges encountered in our earlier studies. Our findings, including insights into the impact of NH2 radicals, contribute to an understanding of ammonia combustion and its potential in achieving carbon-neutral energy systems.
期刊介绍:
As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.