{"title":"H2 + N2O反应的理论分析","authors":"Clayton R. Mulvihill","doi":"10.1016/j.combustflame.2025.114330","DOIUrl":null,"url":null,"abstract":"<div><div>The reaction of H<sub>2</sub> and N<sub>2</sub>O to directly form H<sub>2</sub>O and N<sub>2</sub> has been a matter of some controversy, with reported rate constants spanning nearly five orders of magnitude at 1500 K. This study presents the first theoretical analysis of the title reaction. By coupling an ANL1-QZF potential energy surface with a master equation treatment, the pressure-independent thermal rate constant <span><math><msub><mi>k</mi><mn>1</mn></msub></math></span> was determined between 400 and 3000 K. The best-fit <span><math><msub><mi>k</mi><mn>1</mn></msub></math></span> is given in cm<sup>3</sup>·mol<sup>–1</sup>·s<sup>–1</sup> as <span><math><mrow><msub><mi>k</mi><mn>1</mn></msub><mo>=</mo><mn>5.23</mn><mspace></mspace><mo>×</mo><msup><mrow><mn>10</mn></mrow><mn>4</mn></msup><mspace></mspace><msup><mrow><mi>T</mi></mrow><mrow><mn>2.272</mn></mrow></msup><mrow><mspace></mspace><mtext>exp</mtext></mrow><mi></mi><mrow><mo>(</mo><mrow><mo>−</mo><mn>21745</mn><mo>/</mo><mi>T</mi></mrow><mo>)</mo></mrow></mrow></math></span>, with <span><math><mi>T</mi></math></span> in K. This rate constant is several orders of magnitude smaller than values utilized in recent kinetics mechanisms.</div></div>","PeriodicalId":280,"journal":{"name":"Combustion and Flame","volume":"279 ","pages":"Article 114330"},"PeriodicalIF":5.8000,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A theoretical analysis of the reaction H2 + N2O ⇆ H2O + N2\",\"authors\":\"Clayton R. Mulvihill\",\"doi\":\"10.1016/j.combustflame.2025.114330\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The reaction of H<sub>2</sub> and N<sub>2</sub>O to directly form H<sub>2</sub>O and N<sub>2</sub> has been a matter of some controversy, with reported rate constants spanning nearly five orders of magnitude at 1500 K. This study presents the first theoretical analysis of the title reaction. By coupling an ANL1-QZF potential energy surface with a master equation treatment, the pressure-independent thermal rate constant <span><math><msub><mi>k</mi><mn>1</mn></msub></math></span> was determined between 400 and 3000 K. The best-fit <span><math><msub><mi>k</mi><mn>1</mn></msub></math></span> is given in cm<sup>3</sup>·mol<sup>–1</sup>·s<sup>–1</sup> as <span><math><mrow><msub><mi>k</mi><mn>1</mn></msub><mo>=</mo><mn>5.23</mn><mspace></mspace><mo>×</mo><msup><mrow><mn>10</mn></mrow><mn>4</mn></msup><mspace></mspace><msup><mrow><mi>T</mi></mrow><mrow><mn>2.272</mn></mrow></msup><mrow><mspace></mspace><mtext>exp</mtext></mrow><mi></mi><mrow><mo>(</mo><mrow><mo>−</mo><mn>21745</mn><mo>/</mo><mi>T</mi></mrow><mo>)</mo></mrow></mrow></math></span>, with <span><math><mi>T</mi></math></span> in K. This rate constant is several orders of magnitude smaller than values utilized in recent kinetics mechanisms.</div></div>\",\"PeriodicalId\":280,\"journal\":{\"name\":\"Combustion and Flame\",\"volume\":\"279 \",\"pages\":\"Article 114330\"},\"PeriodicalIF\":5.8000,\"publicationDate\":\"2025-07-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Combustion and Flame\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0010218025003670\",\"RegionNum\":2,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENERGY & FUELS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Combustion and Flame","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0010218025003670","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENERGY & FUELS","Score":null,"Total":0}
A theoretical analysis of the reaction H2 + N2O ⇆ H2O + N2
The reaction of H2 and N2O to directly form H2O and N2 has been a matter of some controversy, with reported rate constants spanning nearly five orders of magnitude at 1500 K. This study presents the first theoretical analysis of the title reaction. By coupling an ANL1-QZF potential energy surface with a master equation treatment, the pressure-independent thermal rate constant was determined between 400 and 3000 K. The best-fit is given in cm3·mol–1·s–1 as , with in K. This rate constant is several orders of magnitude smaller than values utilized in recent kinetics mechanisms.
期刊介绍:
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