Grant for Exploratory Research: High-Pressure Photoacoustic Calorimetry

这项用于探索性研究的小额赠款由无机化学、生物无机化学和金属有机化学计划提供，以支持高压光声热计的开发和应用。孟菲斯州立大学化学系的Theodore J.Burkey博士将建造一个池，在其中进行有机金属化合物的反应，并测量由于反应物和中间体或产品的体积不同而导致的体积变化。该方法将有助于确定光引发反应的详细反应机理，包括取代反应和烷烃和其他小分子的活化。该项目被视为有风险，因为该方法可能不够敏感。如果成功，该方法可能有助于研究尚未被广泛研究的有机金属反应，并将结果与用于确定活化量的少数其他方法进行比较。在反应过程中，反应物和溶剂分子都会重新排列成反应所需的最佳方向。由于这种重排，反应物的体积在反应过程中发生了变化。产物的体积也与反应物的体积不同。因此，对反应过程中体积变化的测量提供了有关反应所需能量和空间位阻的信息。在该奖项的支持下，西奥多·J·伯基博士将尝试开发一种测量体积变化的新方法，并将获得一些重要的有机金属反应的信息，包括一些催化和一些光诱导过程。

This Small Grant for Exploratory Research is made by the Inorganic, Bioinorganic, and Organometallic Chemistry Program to support the development and application of high pressure photoacoustic calorimetry. Dr. Theodore J. Burkey of the Chemistry Department, Memphis State University, will construct a cell in which to carry out reactions of organometallic compounds and measure the change in volume due to differences in the volumes of reactants and intermediates or products. The method will be useful in determining detailed reaction mechanisms for photointiated reactions, including substitution reactions and activation of alkanes and other small molecules. The project is viewed as risky since the method may not be sufficiently sensitive. If successful, the method could be useful for studying organometallic reactions, whose mechanisms have not been extensively studied, and for comparison of results with the few other methods used for determining volumes of activation. %%% During the course of reactions, both reactant and solvent molecules rearrange themselves to optimal orientations required for reaction. As a result of this rearrangement, the volume of the reactants changes during the course of the reaction. The volume of the products also differs from that of the reactants. Thus, measurement of volume change during reaction provides information about the energy and steric requirements for reaction. With the support of this award, Dr. Theodore J. Burkey will attempt to develop a new method for measuring volume changes and will gain information on a number of important organometallic reactions, including some catalytic and some light induced processes.