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.

北卡罗来纳大学阿什维尔分校的伯特·霍姆斯和乔治·赫德在实验物理化学项目的支持下，对化学活化的氢卤代烷烃的单分子反应动力学进行了合作实验和理论研究。 这项研究建立在 PI 之前对一种不寻常的气相机制的研究基础上，该机制涉及相邻碳上的卤素交换。 该计划以氢卤烷为重点，确定各种 1,2 卤素交换反应和 1,2-HX（其中 X = F、Cl 或 Br）消除反应的阈值能垒以及取代基对这些能垒的影响。 电子结构计算将给出反应物和过渡态的频率和惯性矩，这些将与 RRKM 理论一起使用来计算速率常数并允许分析结构-反应性关系的趋势。 该项目的研究成果可以提高对涉及氢氯氟碳化合物的燃烧、焚烧和大气化学过程的理解。 这项研究预计将提供充足的机会，通过让学生参与旨在培养分析思维技能和解决问题能力的研究，并鼓励他们追求化学科学高级工作的兴趣，从而提供充足的机会来加强本科教育。