Kinetics and Mechanisms of Main-Group Reactions

主族反应的动力学和机理

• 批准号: 9220924
• 负责人: David Stanbury
• 金额: $ 32万
• 依托单位: Auburn University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-12-01 至 1996-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9220924&HistoricalAwards=false
• 关键词: Kinetics; Mechanisms; Main; Group; Reactions

This project is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program. Its focus is the kinetics and mechanisms of main-group inorganic reactions in aqueous solution. Stopped-flow methods (with single wavelength, rapid scan and conductivity detection) will be used to obtain kinetic data. The stopped-slow data will be used to obtain rate constants, reaction rate laws and stoichiometries. Reactions to be studied include: 1) Selected electron transfer reactions between pairs of main-group redox couples, in order to provide stringent tests of the applicability of Marcus theory to reactions between species of widely differing ionic radii; 2) electron transfer reactions involving chlorine/dichloride, bromine/dibromide, hydroxylammonium/hydroxylamine, and NO/NO- as redox couples, where the reaction partners are substitution-inert coordination complexes, leading to standard redox potentials and effective self-exchange rate constants for the main-group couples; 3) dihydrogen transfer from diimide (now that methods are available to generate and detect this species) with emphasis on reactions with dioxygen, diiodine and hydrogen peroxide, as well as with olefins and one-electron oxidants; 4) inner-sphere reactions in which sulfite is oxidized by tetrachloroaurate(III) and other coordination complexes, probing the mechanistic factors that lead to formation of the S-S bond in dithionate; 5) the reactions of NO with dioxygen and of sulfur trioxide with water, because of their relevance to environmental issues. %%% Reactions of molecules containing the so-called main-group elements, such as nitrogen, sulfur, chlorine and bromine, are of great importance in industry and in everyday life, with examples including the purification of drinking water and the action of chlorine bleach in the home washing machine. In addition to providing a better understanding of how many of these common reactions occur, the results of this project may provide insight into how to avoid detrimental side reactions, such as the formation on carcinogens during the chlorination of sewage plant effluents.

该项目得到了无机、生物无机和有机金属化学项目的支持。 其重点是水溶液中主族无机反应的动力学和机理。将使用停流方法（单波长、快速扫描和电导率检测）来获取动力学数据。 停止慢速数据将用于获得速率常数、反应速率定律和化学计量。 要研究的反应包括： 1）选定的主族氧化还原对之间的电子转移反应，以便严格检验Marcus理论对不同离子半径的物种之间的反应的适用性； 2）涉及氯/二氯化物、溴/二溴化物、羟铵/羟胺和NO/NO-作为氧化还原对的电子转移反应，其中反应伙伴是取代惰性配位络合物，导致主族对的标准氧化还原电位和有效自交换速率常数； 3）二酰亚胺的二氢转移（现在已有方法可以生成和检测该物质），重点是与分子氧、二碘和过氧化氢以及与烯烃和单电子氧化剂的反应； 4）亚硫酸盐被四氯金酸盐（III）和其他配位化合物氧化的内球反应，探讨连二硫酸盐中S-S键形成的机理因素； 5) NO 与分子氧的反应以及三氧化硫与水的反应，因为它们与环境问题相关。 %%% 含有所谓主族元素（如氮、硫、氯和溴）的分子的反应在工业和日常生活中非常重要，例如饮用水的净化和家用洗衣机中氯漂白剂的作用。除了更好地了解这些常见反应的发生数量之外，该项目的结果还可以深入了解如何避免有害的副反应，例如污水厂废水氯化过程中致癌物的形成。