{"title":"H 原子与硫化羰基反应的温度相关速率常数","authors":"Yuri Bedjanian","doi":"10.1002/kin.21700","DOIUrl":null,"url":null,"abstract":"<p>The kinetics of the reaction of H-atom with carbonyl sulfide (OCS) has been investigated at nearly 2 Torr total pressure of helium over a wide temperature range, <i>T</i> = 255–960 K, using a low-pressure discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer. The rate constant of the reaction H + OCS → SH + CO (1) was determined under pseudo-first order conditions, monitoring the kinetics of H-atom consumption in excess of OCS, <i>k</i><sub>1</sub> = 6.6 × 10<sup>−13</sup> × (<i>T</i>/298)<sup>3</sup> × exp(−1150/<i>T</i>) cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup> (with estimated total uncertainty on <i>k</i><sub>1</sub> of 15% at all temperatures). Current measurements of <i>k</i><sub>1</sub> at intermediate temperatures (520–960 K) appear to reconcile previous high and low temperature data and allow the above expression for <i>k</i><sub>1</sub> to be recommended for use in the extended temperature range between 255 and 1830 K with a conservative uncertainty of 20%.</p>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2023-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Temperature dependent rate constant for the reaction of H-atoms with carbonyl sulfide\",\"authors\":\"Yuri Bedjanian\",\"doi\":\"10.1002/kin.21700\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The kinetics of the reaction of H-atom with carbonyl sulfide (OCS) has been investigated at nearly 2 Torr total pressure of helium over a wide temperature range, <i>T</i> = 255–960 K, using a low-pressure discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer. The rate constant of the reaction H + OCS → SH + CO (1) was determined under pseudo-first order conditions, monitoring the kinetics of H-atom consumption in excess of OCS, <i>k</i><sub>1</sub> = 6.6 × 10<sup>−13</sup> × (<i>T</i>/298)<sup>3</sup> × exp(−1150/<i>T</i>) cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup> (with estimated total uncertainty on <i>k</i><sub>1</sub> of 15% at all temperatures). Current measurements of <i>k</i><sub>1</sub> at intermediate temperatures (520–960 K) appear to reconcile previous high and low temperature data and allow the above expression for <i>k</i><sub>1</sub> to be recommended for use in the extended temperature range between 255 and 1830 K with a conservative uncertainty of 20%.</p>\",\"PeriodicalId\":13894,\"journal\":{\"name\":\"International Journal of Chemical Kinetics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2023-10-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"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.21700\",\"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.21700","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
利用低压放电流反应器和电子碰撞电离四极杆质谱仪,研究了 H 原子与硫化羰基(OCS)在接近 2 托的氦气总压和较宽的温度范围(T = 255-960 K)内的反应动力学。在伪一阶条件下测定了 H + OCS → SH + CO (1) 反应的速率常数,监测了过量 OCS 消耗 H 原子的动力学,k1 = 6.6 × 10-13 × (T/298)3 × exp(-1150/T) cm3 molecule-1 s-1(在所有温度下,k1 的总不确定性估计为 15%)。目前在中间温度(520-960 K)下对 k1 的测量结果似乎与之前的高温和低温数据相吻合,因此建议在 255 至 1830 K 的扩展温度范围内使用上述 k1 表达式,保守的不确定性为 20%。
Temperature dependent rate constant for the reaction of H-atoms with carbonyl sulfide
The kinetics of the reaction of H-atom with carbonyl sulfide (OCS) has been investigated at nearly 2 Torr total pressure of helium over a wide temperature range, T = 255–960 K, using a low-pressure discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer. The rate constant of the reaction H + OCS → SH + CO (1) was determined under pseudo-first order conditions, monitoring the kinetics of H-atom consumption in excess of OCS, k1 = 6.6 × 10−13 × (T/298)3 × exp(−1150/T) cm3 molecule−1 s−1 (with estimated total uncertainty on k1 of 15% at all temperatures). Current measurements of k1 at intermediate temperatures (520–960 K) appear to reconcile previous high and low temperature data and allow the above expression for k1 to be recommended for use in the extended temperature range between 255 and 1830 K with a conservative uncertainty of 20%.
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.