RUI: Experimental and Theoretical Investigation of Threshold Energy Barriers and Substituent Effects for the 1,2-Halogen Interchange Reaction in Haloalkanes

RUI：卤代烷烃中 1,2-卤素交换反应的阈值能垒和取代基效应的实验和理论研究

• 批准号: 0647582
• 负责人: George Heard
• 金额: $ 27.1万
• 依托单位: University of North Carolina at Asheville
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-06-01 至 2012-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0647582&HistoricalAwards=false
• 关键词: RUI; Experimental; Theoretical; Investigation; Threshold

Bert Holmes and George Heard of the University of North Carolina at Asheville are supported by the Experimental Physical Chemistry Program to carry out a collaborative experimental and theoretical study of the kinetics of unimolecular reactions of chemically activated hydrohaloalkanes. The research builds on the PIs' previous investigations of an unusual gas phase mechanism involving the exchange of halogens on adjacent carbons. Focusing on hydrohaloalkanes, the plan is to determine threshold energy barriers and the effect of substituents on these energy barriers for various 1,2 halogen interchange reactions and for the 1,2-HX (where X = F, Cl, or Br) elimination reaction. Electronic structure calculations will give the frequencies and moments of inertia of the reactant and transition state, and these will be used with RRKM theory to calculate rate constants and permit the analysis of trends in the structure-reactivity relationships. Research outcomes from this project could improve the understanding combustion, incineration, and atmospheric chemical processes involving hydrochlorofluorocarbons. This research is expected to provide ample opportunities to enhance undergraduate education by involving students in research that is designed to develop analytical thinking skills and problem-solving ability, and encourage interest in pursuing advanced work in the chemical sciences.

伯特·福尔摩斯（Bert Holmes）和乔治（George）听说了阿什维尔（Asheville）的北卡罗来纳大学（University of Asheville）的实验化学化学计划的支持，以对化学激活的水词反应的非分子反应动力学进行协作实验和理论研究。 该研究基于PIS先前对涉及相邻碳卤素交换的异常气相机制的研究。 该计划的重点是确定阈值能量屏障以及取代基对各种1,2卤素互换反应以及1,2-HX（其中X = F，Cl或Br）消除反应的影响。 电子结构计算将给出反应物和过渡状态的惯性的频率和矩，并且这些计算将与RRKM理论一起使用，以计算速率常数并允许分析结构反应性关系中的趋势。 该项目的研究结果可以改善涉及氢氟化合物的理解燃烧，焚化和大气化学过程。 预计这项研究将提供充足的机会来增强本科教育，通过让学生参与研究，旨在发展分析思维技能和解决问题的能力，并鼓励人们兴趣从事化学科学领域的先进工作。