{"title":"高温下H + N2O和NH + NO反应激发OH生成动力学","authors":"Akira Matsugi*, ","doi":"10.1021/acs.jpca.5c04409","DOIUrl":null,"url":null,"abstract":"<p >The reactions H + N<sub>2</sub>O → N<sub>2</sub> + OH* (R1) and NH + NO → N<sub>2</sub> + OH* (R2) have been proposed as sources of the electronically excited OH(A<sup>2</sup>Σ<sup>+</sup>) radicals, denoted as OH*, during combustion of nitrogen-containing compounds. The present study investigates the kinetics of these reactions through OH* emission experiments using a shock tube. Time profiles of OH* concentration measured for several shock-heated mixtures are analyzed with the help of kinetic simulations. The rate constants for R1 are determined using the profiles obtained from H<sub>2</sub>/N<sub>2</sub>O/Ar, NH<sub>3</sub>/N<sub>2</sub>O/Ar, and C<sub>2</sub>H<sub>5</sub>I/N<sub>2</sub>O/Ar mixtures and can be expressed as <i>k</i><sub>1</sub> = (8.4 ± 3.8) × 10<sup>–11</sup> exp(−22900 K/<i>T</i>) cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup> over the temperature range of <i>T</i> = 1600–2200 K. For R2, the rate constants are obtained from the measurements for NH<sub>3</sub>/NO/Ar and NH<sub>3</sub>/N<sub>2</sub>O/NO/Ar mixtures and are represented as <i>k</i><sub>2</sub> = (1.6 ± 0.8) × 10<sup>–13</sup> exp(−10040 K/<i>T</i>) cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup> over 2000–2600 K. Possible mechanisms for the formation of OH* are discussed based on a comparison of the rate constants.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 31","pages":"7208–7217"},"PeriodicalIF":2.8000,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Kinetics of Excited OH Formation in H + N2O and NH + NO Reactions at High Temperatures\",\"authors\":\"Akira Matsugi*, \",\"doi\":\"10.1021/acs.jpca.5c04409\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The reactions H + N<sub>2</sub>O → N<sub>2</sub> + OH* (R1) and NH + NO → N<sub>2</sub> + OH* (R2) have been proposed as sources of the electronically excited OH(A<sup>2</sup>Σ<sup>+</sup>) radicals, denoted as OH*, during combustion of nitrogen-containing compounds. The present study investigates the kinetics of these reactions through OH* emission experiments using a shock tube. Time profiles of OH* concentration measured for several shock-heated mixtures are analyzed with the help of kinetic simulations. The rate constants for R1 are determined using the profiles obtained from H<sub>2</sub>/N<sub>2</sub>O/Ar, NH<sub>3</sub>/N<sub>2</sub>O/Ar, and C<sub>2</sub>H<sub>5</sub>I/N<sub>2</sub>O/Ar mixtures and can be expressed as <i>k</i><sub>1</sub> = (8.4 ± 3.8) × 10<sup>–11</sup> exp(−22900 K/<i>T</i>) cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup> over the temperature range of <i>T</i> = 1600–2200 K. For R2, the rate constants are obtained from the measurements for NH<sub>3</sub>/NO/Ar and NH<sub>3</sub>/N<sub>2</sub>O/NO/Ar mixtures and are represented as <i>k</i><sub>2</sub> = (1.6 ± 0.8) × 10<sup>–13</sup> exp(−10040 K/<i>T</i>) cm<sup>3</sup> molecule<sup>–1</sup> s<sup>–1</sup> over 2000–2600 K. Possible mechanisms for the formation of OH* are discussed based on a comparison of the rate constants.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\"129 31\",\"pages\":\"7208–7217\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2025-07-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.5c04409\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.5c04409","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Kinetics of Excited OH Formation in H + N2O and NH + NO Reactions at High Temperatures
The reactions H + N2O → N2 + OH* (R1) and NH + NO → N2 + OH* (R2) have been proposed as sources of the electronically excited OH(A2Σ+) radicals, denoted as OH*, during combustion of nitrogen-containing compounds. The present study investigates the kinetics of these reactions through OH* emission experiments using a shock tube. Time profiles of OH* concentration measured for several shock-heated mixtures are analyzed with the help of kinetic simulations. The rate constants for R1 are determined using the profiles obtained from H2/N2O/Ar, NH3/N2O/Ar, and C2H5I/N2O/Ar mixtures and can be expressed as k1 = (8.4 ± 3.8) × 10–11 exp(−22900 K/T) cm3 molecule–1 s–1 over the temperature range of T = 1600–2200 K. For R2, the rate constants are obtained from the measurements for NH3/NO/Ar and NH3/N2O/NO/Ar mixtures and are represented as k2 = (1.6 ± 0.8) × 10–13 exp(−10040 K/T) cm3 molecule–1 s–1 over 2000–2600 K. Possible mechanisms for the formation of OH* are discussed based on a comparison of the rate constants.
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The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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